Designation: D3230- 19 Standard Test Method for Salts in Crude Oil (Electrometric Method)! ‘This staid isd under the fed eignsin D323 the manber immediatly olonng te desigaion ines the year of vial ain onthe ae of vison, he yar of ast rvison. A ane pennies heer ot ane ‘supencip epilon () dates an eto chatie since the lan evo oop Drv sandard has hen approved for te by agen of the US. Bement of Defence 1. Scope* 1.1 This test method covers the determination of the ‘approximate chloride (salts) concentration in crude oil. The range of concentration covered is 3.5 mg/ke to 500 mg/kg or 1.0'1b/1000 bbl to 150 1b/1000 ‘bbl (PTB) as chloride concentration/volume of crude oil 1.2 This test method measures conductivity inthe crude vil due to the presence of common chlorides, such as sodium, calcium, and magnesium, Other conductive materials may also be present in the crude oil 1.3 The values stated in SI units are to be regarded as Standard. No other units of measurement are included in this standard, 1.3.1 Exception—Acceptable concentration units are g/m? or PTB (16/1000 bb) 14 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of tis standard to establish appro priate safety, health, and environmental practices and deter- ‘mine the applicability of regulatory limitations prior to use. For specific warning statements, sce 7.3, 7.4, and 7.11 15 This international standard was’developed in accor- dance with internationally recognized principles on standard- ization established in the Decision on Principles for the Development of International Standards, Guides and Recom= ‘mendations issued by the World Trade Organization Technical Barriers 10 Trade (TBT) Committe, 2. Referenced Documents 2.1 ASTM Standards: D381 Test Method for Gum Content in Fuels by Jet Evapo- ration "This tes method is under the justin of ASTM Commitee 02 oa ‘ole Products, Lig Ful snd Lic an isthe ie apoyo Sucomminee B02 03 on Elemental Araya, Centon apposed May 1. 20. Published May. 201 Originally ‘aproved in 1978 Last previous edon approved in 2018 a D3230 [3 GOI8) Dor 1o1smp i019 "For referenced ASTM sada, visit the ASTM website, wwastm or, or ‘one ASTM Custer Service at sven ny For Ana Boot of TIE Starla vom information, retro wandad' Docent Sumer page (ie ASTM wei D1193 Specification for Reagent Water 'D4928 Test Method for Water in Crude Oils by Coulometric Karl Fischer Titration 15002 Test Method for Density, Relative Density, and API Gravity of Crude Oils by Digital Density Analyzer 3. Terminology 311 Definitions of Terms Specific to This Standard: 3.1.1 PTB—1b/1000 bb, 3.1.2 salts in crude oil—commonly, chlorides of sodium, calcium, and magnesium dissolved in crude oil, Other inor- ganic chlorides may also be present. 4, Summary of Test Method 4.1 ‘This test method measures the conductivity ofa solution of crude oil in a mixed alcohol solvent when subjected to an electrical stress. This test method measures conductivity due to the presence of inorganic chlorides, and other conductive ‘material, in the crude oil. A homogenized test specimen is dissolved in a mixed alcohol solvent and placed in a test cell consisting of a beaker and a set of electrodes, A voltage is impressed on the electrodes, and the resulting current flow is ‘measured. The chloride (salt) content is obtained by reference toa calibration curve of current versus chloride concentration of known mixtures, Calibration curves are based on standards prepared to approximate the type and concentration of chlo- rides in the crude oils being tested S. Significance and Use 5.1 This test method is used to determine the approximate chloride content of crude oils, a knowledge of which is important in deciding whether ‘or not the crude oil needs desalting. The efficiency of the process desalter can also be evaluated, 5.2 Excessive chloride left in the crude oil frequently results in higher corrosion rates in refining units and also. has otrimental effects on catalysts used in these units 5.3 This test method provides a rapid and convenient means of determining the approximate content of chlorides in crude oil and is useful to crude oil processors *A.Sommary of Changes section appears atthe end ofthis standard evyor © ASTM ronal 10 Ba Hr De FO Bx TE, We Cansahocen PA 1420-28, ed SeeAp 03230 - 19 Apparatus. 6.1 ‘The apparatus (see Annex Al) shall consist of a control unit capable of producing and displaying several voltage levels for applying stress to a set of electrodes suspended in a test beaker containing a test solution. The apparatus shall be capable of measuring and displaying the current (mA) con= ducted through the test solution between the electrodes at each voltage level [Nom 1—Some apparatus are capable of measuring vollage and curent inwerally and, after comparison to internal calibration curves of spay Ing the resultant concent 6.2 Test Beaker—See Annex Al 63 Pipe, 10 mL. (total delivery), shall be used in 10.3 and 11.1 when the viscosity of the crude oil material being analyzed is suitable to transfer the required volume for use in the test (see 6:3.1). The type of pipet to use is one that is able to be rinsed to ensure the entire volume of the material is contained in the intended volume. 6.3.1 In some cases, the viscosity of the crude oil makes it ifficult and impractical to transfer 10 mL. of sample using a pipet. In such cases, itis permissible to use a 10 mL graduated tylinder in place of the pipet to transfer the neutral oil (10.3) and crude oil sample (1.1) to ensure consistency. The current Precision statements are based on the use of 10 mL pipets only. 64 Cylinders, 100 mL, sloppeted. 6.5 Other volumetric and graduated pipets and volumetric asks. 7. Reagents and Materials 7.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests, Unless otherwise indicated, it is intended that all reagents shall conform to the specifications of the American Chemical Society, where such specifications are available.” Other grades may be used, provided itis frst ascertained that the reagent is of sufficiently high purity to permit its usc without lessening the accuracy of the determination 7.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water as defined by Type If in Specification D1193, 7.3 Mixed Alcohol Solvent—Mix 63 volumes of 1-butanot and 37 volumes of absolute methyl alcohol (anhydrous). To each litre of this mixture, add 3 ml. of water. (Warning— Flammable, Liquid causes eye burns. Vapor harmful. May be fatal or cause blindness if swallowed or inhaled.) Now: 2—The mixed alcohol solvent is suitable for use if ts conduc- fivty is less than 025mA\at 125 V ac (or 2 inicrosiemens) High conductivity can be de to excess water inthe solvent and ca indica that the met sleohol used is not antycrous, 74 Hexanes, Reagent Grade, (Warning—Extremely flammable, harmful if inhaled.) "Reagent Chemica American Chemical Society Spcitstions. American ‘Chemie Sci Washington. DC. Fr Supgeson nthe esing of eapet listed bythe American Chemical Society. se Anal Stndara for Laboratory Chemie, BDI Li Pole, Dove UX, andthe Una Ses Prmapele and KationelFormaars US. Phawacoeit Convio. In. (USPC), Rockvil, Mb. Nort 3—Hesanes solvents sometimes refered tor sold hy other names, such as petroleum naphtha, petroleum ether, ligrine,perleury benzin, and industrial naphtha. One should confirm that it mets the requirements of 74 7.5 Calcium Chloride (CaCl) Solution (10 gA.)—Transfer 100g * 0.01 of CaCl, oF the equivalent weight of a hydrated salt, into a 100 mL volumetric flask and dissolve in 25 mL of water. Dilute to the mark with mixed alcohol solvent. 7.6 Magnesium Chloride (MgCl,) Solution (10 g/.)— ‘Transfer 1.00 g + 0.01 g of MgCl, or the equivalent weight of a hydrated salt, into 100 mL. volumetric flask and dissolve in 25 mL of water. Dilute to the mark with mixed alcohol solvent 7.7 Sodium Chloride (NaCl) Solution (10 g/.)—Transfer 1.00 g * 0.01 g of NaCl into a 100 mL. volumetric flask and dissolve in 25 mL of water, Dilute to the mark with mixed alcohol solvent, 7.8 Oil, Refined Newral—Any refined chloride-free oil of approximately 20 mm/sec (cSt) viscosity at 40 °C and free of additive, 7.9 Salts, Mixed Solution (Concentrated Solution)— Combine 10.0 mL of the CaCl, solution, 20.0 mL of the MgCly Solution, and 70.0 mL of the NaCI solution, and mix thor. ‘oughly Nom. 4—The 10:20-70 proprtons are representative othe chlorides present ina numberof common crude cls. When the relative proportions ‘of calcium, magnesium, and sodium chlries are known fora given crude cil, such proportions should he used for most the securate resus 7.10 Salts, Mixed Solution (Dilute Solution)—Transfer 10 mL, of the concentrated mixed chlorides solution into a 1000 mL volumetric flask, and dilute to the mark with mixed alcohol solvent. 7.11 Xplene, reagent grade, minimum purity. (Warning— Flammable. Vapor harmful) 8. Sampling 8.1 Obtain a sample and test specimen in accordance with ‘Test Method D4928, Ensure that the sample is completely homogenized with a suitable mixer, See Test Method D4928 for suitable apparatus and proving, 8.2 Samples of very viscous materials may be warmed until they are reasonably fluid before they are sampled; however, no sample shall be heated more than is necessary to lower the Viscosity to a manageable level 8.3 Samples of crude oil contain water and sediment and are inhomogeneous by nature. The presence of water and sediment will influence the conductivity of the sample, The utmost care shall be taken in obtaining homogenized representative samples, 9. Preparation of Apparatus 9.1 Support the apparatus on a level, steady surface, such as a table 9.2 Prepare the apparatus for operation in accordance with the manufacturer's instructions for calibrating, checking, and ‘operating the equipment. (Warning—The voltage applied to the electrodes can be as great as 250 V ac, and hazardous.)ly 03230 - 19 9.3 Thoroughly clean and dry all pars ofthe test beaker, the electrodes, and its accessories hefore starting the test, being sure to remove any solvent that had been used to clean the apparatus, 10. Calibration 10.1 The conductivity of solutions is affected by the tem- perature of the specimen when measurements are made, The {temperature of the test specimen at the time of measurement shall be within 3 °C of the temperature at which the calibration ‘curves were made, 10.2 Establish a blank measurement by following the pro- cedure in 10.3 and 10.4, omitting the mixed salts solution, ‘When the indicated electrode current is greater than 0.25 mA at 125 V ac, water or another conductive impurity is present and its source must be found and eliminated before calibration can ‘be completed. Determine a blank measurement each time fresh xylene or mixed solvent is used, 10.3 Into a dry, 100 mL graduated, glass-stoppered mixing ylinder, add 15 mL of xylene, From a 10-mL. pipet (total Aelivery, see 6.3), or 10 mL graduated cylinder (see 6.3.1) when applicable, add 10 mL of neutral oil. Rinse the 10 mL. pipet or 10 mL graduated cylinder with xylene until free of oil Make up to 50 mL with xylene, Stopper and shake the cylinder Vigorously for approximately 60's to effect solution. Add a guantity of dilute mixed salts solution, in accordance with Table 1, that is appropriate to the range of salt contents to be ‘measured. Dilute to 100 mL with mixed alcohol solvent. Again shake the cylinder vigorously for approximately 30 s to effect solution, and allow the solution to stand approximately 5 min, Pour the solution into a dry test beaker. 10.4 Immediately place the electrodes into the solution in the beaker, making sure that the upper edge of the electrode Plates are’ below the surface of the solution. Adjust the indicated electrode voltage to a series of values, for example 25'¥. 50 V, 125 V, 200 V, and 250 V ac. At each voltage, note the current reading and record the vollage displayed and the ‘current to the nearest 0.01 mA. Remove the electrodes from the Solution, rinse with xylene followed by naphtha, and allow them to dey, ‘Nore 5—With some apparatus, the detailed stings will not be required TABLE 1 Standard Samples ‘Sak, B7I000 bel Wired Sas Sabon of Cre OF ass), mu 79 03 50 38 100 a0 160 a 210 60 20 80 310 a5 5 510 150 90, 60 200 25 0 Bs 2as 00 28 2 1519 80 —_— is so ‘since the electronics are built-in for auto-ranging. Determination ofthe blank and the calibration standard responses ae the same, 10.5 Repeat the procedure in 10.3, using other volumes of ‘mixed salts solution (dilute solution) as needed to cover the range of chloride contents of interest 10.6 Subtract the value obtained for the blank measurement from the indicated current readings of each standard sample, and plot the chloride content (ordinate) against net current (mA) readings (abscissa) for each voltage on 3 by 3 cycle log-log paper, or other suitable format. 'Nom-6—Some apparatus are capable of internally recording the current readings standard concentration, and blank, and they provide an oat in ieet concentration units. Altematively, some apparatun are ano capable Of internally converting. and displaying the measured caren, ino conductivity units of microsiemens, 1S, although the precise of such ‘struments was not evaluated in the 1997 interlaboratory sty hens in Section 14, Precision and Bias. Now 7-—The apparatus are calibrated against standard solutions of ‘neutral ol and mixed chloride solutions in xylene because of the extreme iicalies in keeping erudeoil-brine mixtures homogeneous. The cals bration may be contimed, if desired, by careful replicate analysis of nude-ol samples by exhaustive extaction of sale with hat water followed by titration ofthe chlorides inthe extract. Nort 8—In calibrating over a wide range uf chive concentrations, i may be necessary 10 apply several voltages to obtain curent readings within the limut of the apparatus current level display (0 mA to TO mA) Higher votes are applied for low concentrations and lower volgen aes pple for high concentrations, AL. Procedure 11.1 To a dry, 100 mL graduated, glass-stoppered cylinder, ‘add 15 mL of xylene and, using the same type of volume transferring device used in 10.3 (that is, either a 10 mL pipet (otal delivery, see 6.3), or 10 mL graduated cylinder (see 6.3.1) when applicable), transfer 10 mL of the crude oil sample into the 100 mL graduated, glass-stoppered cylinder. Rinse the 10 mL pipet or 10 mL graduated eylinder with xylene until free of oil, Make up to 50:mL with xylene. Stopper and shake the cylinder vigorously for approximately 60 s, Dilute to 100 ml. with mixed alcohol solvent, and again shake vigorously for approximately 305, After allowing the solution to stand for approximately 5 min, pour it inwo the dry test beaker. 11.2 Follow the procedure in 10.4 to obtain voltage and ‘current readings. Record the indicated electrode current to the nearest 0.01 mA and the nearest voltage (see Note 6). 11.3 Remove the electrodes from the sample solution, and clean the apparatus 12, Caleulation 12.1 Subtract the value obtained for the blank measurement from the value obtained from the specimen measurement to obtain the net current reading. From the calibration graph, read the indicated salt concentration corresponding to the net current (mA) reading of the sample (see Note 6). 12.2 Caleulate the concentration in mg/kg by using the appropriate equation given below: 00x Sah, mgnag = COX o Sal, mgikg = 2853 Yid @ ‘Reticle Ate aoe encore ee coxomano@stacounAly 03230 - 19 ‘measured salt concentration in g/m’, ‘measured salt concentration in PTB, and Specimen density at 15 C in kg/m’ [Now 9—The density of the specimon can be determined hy varkus methods, such as Test Method DSO02 or other density: messuement methods 13, Report 13.1. Report the following information: The concentration in mg/kg as electromettic chloride in crude oil per Test Method 13230, Altemately, report the concentration directly in g/m” or Tb/1000 bbl. if so required, Nore 10—For reporting purposes, the values stated in PTB are the ‘referred units inthe United Sates nother eoutres,tei common unis fan Be used. 14, Precision and Bias* 14.1. Frecision—The precision of this test method as deter- ‘mined by the statistical examination ofthe 1997 interlaboratory {est results is as follows: 14.1.1 Repeatability—The difference between successive results, obtained by the same operator with the same apparatus tunder constant operating conditions on identical test material, ‘would in the long run, in the normal and correct operation of the test method, exceed the following values in one case in twenty. 1 (ome) = 0.3401 x9 @ (tv 1000 but) = O.2581 > o where: X= the average of wo test results in mg/kg, and Supporting da Rave ben fed at ASTM lntertonl Headunes and may ‘be obtained by reyuesing Resear Repo RR:DOD- 147, Coat ASTM Cason Servis a service atm orp Y = the average of two test results in Ib/1000 bbl (PTB). 14.1.2 Reproducibility —The difference between two single {and independent results, obtained by different operators work- ing in different laboratories on identical material, would in the Jong run, exceed the following values in only one case in twenty. or) (16/1000 bo) 2.7803 x8" 2.089 ¥0"" «s o the average of two test results in mg/kg, and the average of two test results in 1b/1000 bbl (PTB). Nom LI—Sine ll instruments in the 1997 interlaboratory cooperative test program were calibrated in PTB and results reported in PTB, the brecision statement was ively obwined in PTR. The resulig previon ‘data have been mathematically converted into. precision i mele, assuming an average density ofthe erude oil samples of 0895 ket, 14.2 Bias~The procedure in Test Method D3230 has no bias since salt content is defined only in terms of this test ‘method and certified reference materials are unavailable. However, since the samples from the interlaboratory study ‘were neat desalted crudes, spiked with known quantities of salt (as sea water and formation water), bias might be defined as Percent recovery of halide added. Over the range from $ g/n* {to 500 g/m* (1.5 PTB to 150 PTB) salt added, the recovery Proved to be approximately constant and averaged 93 %, 14.3 The precision statements were derived from a 1997 interlaboratory cooperative test program, Participants analyzed eight sample sets comprised of crude oils with various concen- trations of chlorides. Thirteen laboratories participated with the commercial available apparatus. See 6.3 and 6.3.1 for addi- tional information about the precision statements 15. Keywords 15.1. chlorides; crude oil; electrometrc; halides; petroleum; salt in erude ANNEX (Mandat Information) AL. APPARATUS ALI Electrometric Chloride Apparatus (Custom Manu- facture) (see Fig. Al.1 and Note Al.1) ALLL Milliammeten, 0 mA to 1 mA de with OmA to 1 mA ac scale, 88.0 internal resistance. AL.L2 Bridge Rectifier, full-wave, 0.75.A capacity at 60 Hz, ambient temperature; minimum of 400 PRV (Peak Reverse Voltage). AL.1.3 AC Voltmeter, rectifier type, 2000 2,0 V t0 300 V range. Al.L4 Variable Voltage Autotransformen input 105 V 10 LTV, S0/60 He, output 0 V to 132 V, 1.75 A capacity ALLS Transformer, plate supply 240 V, center tap, 50/60 Hz, 250 mA de capacity. ALLL Potentiomerer, 25 0, ten turn AL.1.7 Potentiometer, SO ohm, ten turn. Non: ALI—An equivalent part can be substituted in each cas, provided the electrical characteristics of the entre cireuit remain un changed and the inductive effects and stray eurents are avoided AL2 Test Cell Components (Custom Manufacture) (see Fig. A1.2) A121 Beaker, 100 mL tall form without lip, as deseribed for use in Test Method D381 SEEEEETE, pecppeo rn aecnoneogeancon,ly 03230 - 19 1.2.2. Electrode Assembly, as shown in Fig. Al.2 and Fig, AI. The electrodes mounted in parallel position, exactly ‘opposed and 6.4 mm + 0.1 mm apart, and electrically sepa rated by a nylon or TFE-Muorocarbon spacer AL3 Electrometric Chloride Apparatus (Commercial Manufacture)* A131 The apparatus shall consist of a contro! unit capable of producing and displaying several voltage levels for applying Sires 10 a set of electrodes suspended in a test beaker containing a test solution. ‘The apparatus shall be capable of ‘measuring and displaying the current (mA) conducted through the test solution between the electrodes at each voltage level (ce Note 6) Nore A1.2—Some apparatus is capable of measuring vollage and current internally and after comparison to intemal calibration curves, Aisplay the resultant concentration 1.3.2 The actual construction specities of the apparatus, such as voltages wilized and means of displaying or recording the voltage, displaying or recording the current conduction, oF calculating and displaying the calibration curves/specimen ‘measurements, or combination thereof, ate not critical to the application as long as each individual component remains specific to the given manufactured apparatus (see Note 6). ‘Autoformer Pilot Light 2eIT 33, 115 VAC 60 Hertz ALA Test Cell Components (Commercial Manufacture) AL4.1 Beaker, 100 mL tall form without lip, as described for use in Test Method D381, is commonly used; however, ‘minor variations on dimensions are acceptable to accommodate different manufacturing specifics. The beaker purpose is to provide for containment of the specimen, 1.4.2 Electrode Assembly, shown by example in Fig. Al.2 and Fig. 1.3. The electrode assembly dimensional require- ‘ments and means of support in the beaker are not critical to the application as long as each individual component remains specific to the given manufactured apparatus 1 PIT Switch (PRESS TO MAKE) To Electrodes 10 Tum, 5 Watt Potentiometers FIG. A1.1 250 Volt or 540 Volt TransformerSPACER: We LONG, 4". MATERIAL” CAWAS BxSE aceite ELECTRODE SPACER ‘ascaews MATERIAL: NON CoNOUCTOR, SUCH AS NYLON OR SIMILAR ot eso soos FIG. A12 Test Cell thew LE sicoim oma ru, coon Warenaat -NvLOWoRBETTER OIA. ya DE lene MATERIAL ~ 16 GA, STAINLESS SreEL FIG. A1.3 Electrode Assembly ee nen SEES arrrpromee cotcameoenacneily 03230 - 19 SUMMARY OF CHANGES ‘Subcommittee D02.03 has identified the location of sclected changes to this standard since the last issue (3230 ~ 13 (2018)) that may impact the use of this standard. (Approved May 1, 2019.) (1) Revised subsection 1.1 ASTI Intamatoral takes no postion respecting to vay cary patent ih asserted n connection wih any tem menoned {nti stancard, Users ots Standard ara expres acced at datormiaton of eval of ry such pater hawt ‘of tingement of uch gh. are entaly ta own eoporsnay Biren oma Se CCS was ueyco sons. coxnicogatncon ws